Hydrocarbon conversion using nanocrystalline zeolite Y

ABSTRACT

A process for alkylation of a hydrocarbon compound includes providing a catalyst including a zeolite Y having a crystal size of no more than 100 nm, and reacting an alkylatable hydrocarbon with an alkylating agent in the presence of the catalyst under alkylation reaction conditions to provide a gasoline product having a Research Octane Number of over 99.5.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a continuation of U.S. application Ser. No.10/774,774 filed Feb. 9, 2004 and now issued as U.S. Pat. No. 7,361,797,which is a continuation-in-part of U.S. application Ser. No. 10/067,719filed Feb 5, 2002 and now issued as U.S. Pat. No. 6,793,911, which isherein incorporated by reference, and to which priority is claimed.

BACKGROUND

1. Field of the Invention

The present invention is related to a method for conversion ofhydrocarbon compounds, and particularly to the use of a zeolite catalystfor olefin/paraffin alkylation or aromatic alkylation.

2. Background of the Art

Alkylation pertains to the chemical addition of an alkyl group toanother molecule to form a larger molecule. Commercial alkylationprocesses can typically be aromatic alkylation or olefin/paraffinalkylation. Aromatic alkylation typically involves the production ofalkylaromatic compounds (e.g., ethylbenzene, cumene, etc.) by alkylatingan aromatic compound (e.g., benzene) with an olefin (e.g., ethylene,propylene, etc.). Olefin/paraffin alkylation pertains to the reactionbetween a saturated hydrocarbon with an olefin to produce a highlybranched saturated hydrocarbon with a higher molecular weight, forexample, alkylation of isobutane with 2-butene to produce a gasolineproduct having a high octane number.

Unlike the production of gasoline by cracking high molecular weightpetroleum fractions such as gas oil or petroleum residua, alkylationgives a cleaner gasoline product without sulfur or nitrogen impurities.Moreover, alkylate gasoline has little or no aromatic content, which isa further environmental benefit.

Various alkylation processes are known and used throughout the petroleumindustry. For example, alkylation is routinely carried out commerciallyby using liquid acid catalysts such as sulfuric acid or hydrofluoricacid. Alternatively, solid zeolite catalysts have been used. Use ofzeolites avoids the disadvantages of using highly corrosive and toxicliquid acids. However, zeolites can suffer from deactivation caused bycoking. Various processes for alkylating hydrocarbons usingzeolite-containing catalysts are disclosed in U.S. Pat. Nos. 3,549,557and 3,815,004. An alkylation process using an acid solid catalyst usingzeolitic or non-zeolitic material is disclosed in U.S. Pat. No.5,986,158, which is herein incorporated by reference.

Zeolites are porous crystalline materials characterized bysubmicroscopic channels of a particular size and/or configuration.Zeolites are typically composed of aluminosilicate, but zeolitematerials have been made in a wide range of other compositions. Thelatter are commonly referred to as microporous materials. The channels,or pores are ordered and, as such, provide unique properties, which makezeolites useful as catalysts or absorbents in industrial processes. Forexample, zeolites can be used for filtering out smaller molecules, whichbecome entrapped in the pores of the zeolite. Also, zeolites canfunction as shape selective catalysts that favor certain chemicalconversions within the pores in accordance with the shape or size of themolecular reactants or products. Zeolites have also been useful for ionexchange, such as for water softening and selective recovery of heavymetals.

Synthetic zeolites are traditionally made from sources of silica andaluminum (silica and alumina “nutrients”) that react with each other, inthe presence of materials that ensure highly alkaline conditions, suchas water and OH⁻. Other zeolites can be borosilicates, ferrosilicates,and the like. Many of the crystallization steps are conducted in thepresence of an inorganic directing agent, or an organic template, whichinduces a specific zeolite structure that cannot easily be formed in theabsence of the directing agent or template. Many of the organictemplates are quaternary ammonium salts, but can also be linear amines,alcohols, and a variety of other compounds. As a hydroxide, somedirecting agents introduce hydroxyl ions into the reaction system;however, the alkalinity is usually dictated by the amount of sodiumhydroxide (NaOH), potassium hydroxide (KOH), etc. The reaction typicallyinvolves a liquid gel phase in which rearrangements and transitionsoccur, such that a redistribution occurs between the alumina and silicanutrients, and molecular structures are formed which correspond tospecific zeolites. Other metal oxides can also be included, such astitania-silica, boria-silica, etc. Some zeolites can only be made withorganic templates. Other zeolites can only be made by means of aninorganic directing agent. Yet other zeolites can be made either bymeans of a hydrophilic (e.g., inorganic) directing agent or ahydrophobic (organic based) template.

Much of today's hydrocarbon processing technology is based on zeolitecatalysts. Various zeolite catalysts are known in the art and possesswell-arranged pore systems with uniform pore sizes. The term “mediumpore” as applied to zeolites usually refers to zeolite structures havinga pore size of 4-6 angstrom units (Å). “Large pore” zeolites includestructures having a pore size of above 6 to about 12 Å. Since manyhydrocarbon processing reactions at industrially relevant (i.e., high)conversion rates are limited by mass-transfer (specifically,intraparticle diffusion) , a catalyst particle with an ideal porestructure will facilitate transport of the reactants to active catalystsites within the particle and transport of the products out of thecatalyst particle, but still achieve the desired shape selectivecatalysis. Zeolite morphology, i.e., crystal size, is another parameterin diffusion-limited reactions.

Catalysts have a limited life, for example, because of coking. Catalystdeactivation usually requires a reactor shutdown and catalystregeneration. Although the use of two reactors operated in a “swingmode” (i.e., alternating use of reactors wherein one is operated foralkylation while the other is down for regeneration) allows forcontinuous production, it is nevertheless preferable to performalkylation reactions with zeolite catalysts which have a long life so asto minimize the economic losses incurred by reactor shut down andcatalyst regeneration.

SUMMARY

A process for alkylation of a hydrocarbon compound is provided herein.The process comprises providing a catalyst including a zeolite Y havinga crystal size of no more than 100 nm; and reacting an alkylatablehydrocarbon with an alkylating agent in the presence of said catalystunder alkylation reaction conditions to provide an alkylate product.

The process described herein advantageously provides an alkylate productwith a high Research Octane Number (“RON”) as well as an alkylationreaction having a longer run time.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENT(S)

The alkylation method described herein employs a zeolite withultra-small, or nanocrystalline, crystal size, i.e., a crystal size ofno more than about 100 nanometers (“nm”). The nanocrystalline zeolitepossesses several advantages in connection with certain hydrocarbonconversion processes. For example, the effective diffusivity of manyreactants and products is increased.

Secondly, the product selectivity is enhanced for certain processes,especially sequential reactions, where an intermediate product isdesired. For example, ultra-small crystal size can reduce the amount of(1) over-cracking (e.g., the production of C₃/C₄ light gas products fromthe cracking of vacuum gas oil wherein distillate and naphtha productsare the desired products) and (2) unwanted polyalkylation in aromaticalkylation processes. Also, coking, and the associated catalystdeactivation, is reduced for nanocrystalline zeolites by enabling thecoke precursors to leave the catalyst before undergoing retrogressivecondensation reactions.

Thirdly, the activity of the nanocrystalline zeolite catalyst is higherthan for larger zeolite crystal catalysts, as diffusion limitationlimits the accessibility of inner active sites in the latter case,resulting in a higher effective number of active sites per weight ofcatalyst for the nanocrystalline zeolite catalyst.

The method of the invention is described below in connection primarilywith the use of zeolite Y as produced by the method described incommonly owned, copending U.S. application Ser. No. 10/067,719 foralkylation catalysis. Nanocrystalline zeolite Y produced in accordancewith the method of application Ser. No. 10/067,719 has a cubic faujasitestructure with an effective pore diameter of about 7 to 8 Å and a unitcell size of less than 25 Å. The zeolite Y as-synthesized alsopreferably has a silica to alumina mole ratio of less than about 10,often less than about 7. The crystal size of nanocrystalline zeolite Yis no more than about 100 nm, preferably no more than about 50 nm, andmore preferably no more than about 25 nm.

While the synthesis of nanocrystalline zeolite Y can be carried out inthe presence of an organic template, the preferred way, in terms ofcatalyst production costs, is the use of inorganic directing agents.

Nanocrystalline zeolite Y is useful in various hydrocarbon conversionprocesses, such as: aromatic alkylation and transalkylation in theproduction of ethylbenzene or cumene, alkylation of paraffins witholefins for the production of high octane gasoline, hydrocracking ofvacuum gas oil to produce transportation fuels, hydroprocessing formaking lube oil base stocks, preparation of linear alkylbenzenes oralkylnaphthalenes, selective hydrogenation, aromatic nitration, etc.

The method of preparing nanocrystalline zeolite Y includes impregnatinga solid, porous silica-alumina particle or structure with a concentratedaqueous solution of an inorganic micropore-forming directing agentthrough incipient wetness impregnation. The porous silica-aluminamaterial can be amorphous or crystalline. The amount of liquid is lessthan the amount of liquid that would cause surface gelation visible tothe naked eye. The liquid provided to the solid, porous silica-aluminaparticle or structure is absorbed into and wets the interior voids ofthe latter, but does not form a paste-like material with the same. Theliquid includes water, inorganic micropore-forming directing agent andalso, if necessary, an organic template.

The organic template is selected in accordance with the desired product.Typical organic templates useful in zeolite synthesis include quaternaryammonium salts, linear amines and diamines, and alcohols. Morespecifically, particular organic templates include tetramethyl ammoniumhydroxide or salts thereof, tetraethyl ammonium hydroxide or saltsthereof, tetrapropyl ammonium hydroxide or salts thereof, pyrrolidine,hexane-1,6-diamine, hexane-1-6-diol, piperazine, and 18-crown-6 ethers.

The inorganic micropore-forming directing agent provides hydroxide ionsand can be an alkali metal base or an alkaline earth metal base.However, with respect to the preparation of zeolite Y of the presentinvention, preferred micropore-forming directing agents are theinorganic alkali metal hydroxides, and preferably sodium hydroxide(NaOH). No organic templates are used. Since a high pH favors zeolite Yformation over other crystalline phases, as well as rapid nucleation andcrystallization, high concentrations of the caustic directing agent arerequired. For example, when using concentration of 20% (by weight) orless of NaOH, other crystal phases such as cancrinite or zeolite P maybe formed, no conversion might take place, too large zeolite Y crystalsmay be formed, or the conversion might take an unacceptably long periodof time.

It has surprisingly been found that higher concentrations of inorganicdirecting agent significantly reduce the necessary reaction time. Apreferred range of NaOH concentration in aqueous solution is 21% toabout 60% by weight, more preferred is an NaOH concentration of 25% toabout 60% by weight. Most preferred is an NaOH concentration of 45% to50% by weight. Since higher NaOH concentrations result in exceedinglyhigh viscosity and incomplete internal wetting, the intermediateconcentration range represents an optimal level.

To maintain a “dry” material the amount of inorganic directing agentsolution should not exceed 100% of the pore volume of the porousinorganic oxide material, and preferably ranges from about 80% to about100% of the pore volume.

The degree of uniformity of the impregnation is important for successfulcrystallization of zeolite Y. Localized non-uniformity can result innon-zeolite Y by-product formation. To provide suitable mixing on asmall scale (e.g., in the range of several grams to 100 grams) a mortarcan be used to mix the silica-alumina with the solution of themicropore-forming directing agent. On a larger scale, a mixer incombination with a sprayer can be used.

The synthesis mixture of combined porous/amorphous silica-alumina anddirecting agent (NaOH) is then placed in a heating medium and heated toan elevated temperature of from about 50° C. to about 150° C., morepreferably from about 70° C. to about 110° C. Uniform heating of thesynthesis mixture is desired to preclude the formation of large zeolitecrystals.

The synthesis mixture is maintained at the synthesis temperature for atime period sufficient to convert a sufficient amount of thesilica-alumina to zeolite Y. The final framework structure aftercrystallization contains a substantial crystalline content (by weight),typically at least 15%, preferably at least 50% and most preferably fromabout 75% to 100% zeolite. The period of synthesis time can depend uponthe synthesis temperature, lower synthesis temperatures requiring longersynthesis times. Synthesis time can range from 5 minutes to 150 hours,but more typically from 10 minutes to 48 hours, and preferably fromabout 15 minutes to about 30 hours.

After the required synthesis time, the synthesis mixture is preferablyquenched by active cooling. Subsequently, the micropore-formingdirecting agent should be removed from the product to prevent furtherreaction in later treatment steps or during storage. Then, the sodiumshould be removed from the zeolite framework, e.g., by exchange withammonium, using ion exchange techniques well known to those skilled inthe art.

Optionally, the zeolite can be admixed with a matrix, binder, orcatalyst support, material. Such materials include silica, alumina,aluminosilica, titania, zirconia and the like. Preferably the catalystof the invention includes nanocrystalline zeolite Y and about 5% to 40%by weight of refractory oxide binder such as alumina, silica,silica-alumina, titania, zirconia, etc.

The ion-exchanged zeolite preferably has a sodium content of no morethan about 0.2 wt %, more preferably no more than 0.1 wt %, and yet morepreferably no more than about 0.05 wt %.

Nanocrystalline zeolite Y produced in accordance with the method of theinvention has a mesopore to micropore volume ratio ranging from about0.2 to about 6.0, a BET surface area of at least about 275 m²/g and aunit cell size of from about 24.6 Å to about 24.9 Å.

Optionally, a catalytically active metal can be incorporated into thezeolite by, for example, ion-exchange or impregnation of the zeolite, orby incorporating the active metal in the synthesis materials from whichthe zeolite is prepared. The metal can be in a metallic form or combinedwith oxygen (e.g., metal oxide). Suitable catalytically active metalsdepend upon the particular process in which the catalyst is intended tobe used and generally include, but are not limited to, Group VIII metals(e.g., Pt, Pd, Ir, Ru, Rh, Os, Fe, Co, Ni), rare earth “lanthanide”metals (e.g., La, Ce, Pr, etc.), Group IVB metals (e.g., Ti, Zr, Hf),Group VB metals (e.g., V, Nb, Ta), Group VIB metals (e.g., Cr, Mo, W),or Group IB metals (e.g., Cu, Ag, Au). In a preferred embodiment thecatalytic metal is a rare earth metal, preferably lanthanum, or amixture of rare earth metals having a high lanthanum content, with arare earth metal to zeolite mass ratio of at least about 0.04,preferably at least about 0.08. Another catalytic metal is a noblemetal, preferably platinum, with a metal to zeolite mass ratio of atleast about 0.0001, preferably at least about 0.001.

In one embodiment, the method of the present invention employsnanocrystalline zeolite Y as a catalyst for olefin/paraffin alkylation.It has surprisingly been found that use of nanocrystalline zeolite Yhaving a crystal size of no more than 100 nm, preferably no more than 50nm, and more preferably no more than 25 nm, results in longer catalystlife than conventional zeolite Y, and the resulting gasoline product hasa higher RON, typically at least about 99.5.

The catalyst of the invention is particularly suited to be used foralkylating isoalkanes having 4-10 carbon atoms, such as isobutane,isopentane or isohexane or mixtures thereof, with olefins having 2-10carbon atoms, preferably 2-6 carbon atoms, more preferably 3-5 carbonatoms. The alkylation of isobutane with butene or a mixture of butenesconstitutes an attractive embodiment of the process according to theinvention.

In another embodiment the catalyst of the invention can be used for thealkylation of an aromatic compound, such as benzene, with an olefin(e.g., ethylene, propylene, 1-butene, 2-butene, isobutene, etc.) toproduce a corresponding alkylaromatic compound (e.g., ethylbenzene,cumene, di-isopropylbenzene, etc.). Also, the catalyst can be used forthe transalkylation of polyalkylated aromatics with bare ring aromatics(e.g., benzene) to provide monoalkylated aromatics.

As will be evident to the skilled person, the process according to theinvention can be applied in any suitable form, including fluidized bedprocesses, slurry processes and fixed bed processes. The process may becarried out in a number of beds, each with separate olefin addition. Insuch a case, the process of the invention may be carried out in eachseparate bed.

The olefin-paraffin alkylation process is practiced under conditionssuch that at least a portion of the alkylation agent and the alkylatablecompound will be in the liquid phase or the supercritical phase. Ingeneral, the process according to the invention is practiced at atemperature in the range of about −40° C. to about 250° C., preferablyin the range of about 50° C. to about 150° C., more preferably in therange of about 75° C. to about 95° C., and a pressure of from 1 to 100bar, preferably of from 10 to 40 bar, more preferably of from 15 to 30bar. The molar ratio of alkylatable compound to alkylation agent in thetotal feed in the reactor preferably is higher than 5:1, more preferablyhigher than 50:1. The feed rate (WHSV) of the alkylation agent generallyis in the range of 0.01 to 5, preferably in the range of 0.05 to 0.5,more preferably in the range of 0.1 to 0.4 parts of alkylation agent perpart of catalyst per hour. The WHSV of the alkylatable saturatedhydrocarbon preferably is in the range of 0.1 to 500 hr⁻¹.

Another preferred process is aromatic alkylation such as the alkylationof benzene with ethylene to produce ethylbenzene or the alkylation ofbenzene with propylene to produce cumene, which may be carried out in abatch, semi-continuous or continuous fashion.

The examples below illustrate various features of the process of thepresent invention. The comparative examples do not exemplify theinvention but are provided for the purpose of showing by comparison thesurprising improvements achieved by the present invention over the useof conventional zeolite Y catalyst for olefin/paraffin alkylation,particularly, for the alkylation of isobutane with cis-2-butene toproduce gasoline products. In all of the examples the olefin andparaffin were fed into a fixed bed reactor immersed in an oil bath tomaintain a desired temperature. The reactor effluent was divided intotwo portions. One portion of the product was recycled back to thereactor as a recycle stream into which the olefin/paraffin feed wasinjected. Another portion, a product recovery stream, was sent to acondenser for separation of the alkylate product. Samples of the reactoreffluent were drawn off for testing prior to separation of the productstream into a recycle stream and product recovery stream.

One test was performed for the determination of catalyst on-stream lifeby observation of the on-stream time which elapsed before “olefinbreakthrough,” i.e., the point at which 0.2% of the olefin leaves thereactor without being converted. The reactor effluent was monitored bychromatographic analysis to determine when olefin peaks appeared. Thecatalyst life is an important feature since the better the catalystlongevity is, the less the reactor needs to be taken off-line forcatalyst regeneration.

Also, the total RON of the product was monitored. Each component of theproduct stream is characterized by a respective RON. The preferredalkylation products are trimethypentanes (“TMP's”), which have highresearch octane numbers (RON of about 100 to 110). The total RON of thealkylate product, which represents the anti-knock quality of thegasoline, was determined by calculating the weighted average of theRON's of the individual product components.

COMPARATIVE EXAMPLE 1

The zeolite catalyst evaluated in this Comparative Example was acommercially available zeolite HY and containing 70 wt. % zeolite HY inan alumina binder. The zeolite crystal size of this sample was 0.4-0.7microns (i.e., 400-700 nm). The zeolite catalyst was derived from 1/32″extrudates and −18 to +25 mesh with a BET surface area of 562 m²/g. Thetest reactor was a recirculating differential fixed bed reactor in asystem as described above with a feed containing isobutane andcis-2-butene in an isobutane/olefin (I/O) ratio of 15.9 and with a feedrate of 16.2 parts/hr. 4.6 Parts by weight of zeolite catalyst werecharged to the reactor. The catalyst was pretreated in flowing nitrogenat 300° C. for 2 hours to remove moisture before the alkylation test wasbegun.

Alkylation was conducted at 400 psig and 80° C. with a recycle rate of174 parts of the reaction effluent per parts of catalyst per hour. Thetest was carried out with samples taken every 45 minutes for GC analysisuntil olefin breakthrough. The catalyst life, as determined by olefinbreakthrough, for this commercial zeolite Y catalyst was 2.7 hours. TheRON as measured before olefin breakthrough was calculated to be 99.1.These results are summarized in Table 1.

COMPARATIVE EXAMPLE 2

The zeolite catalyst used in this Comparative Example is was 3.6 partsof commercially available zeolite HY and derived from 1/16″ extrudatescontaining 80 wt % zeolite HY in an alumina binder. The zeolite crystalsize of this sample was 0.4-0.7 microns. The dried catalyst was sievedto −18 to +25 mesh with a BET surface area of 556 m²/g. The pretreatmentand alkylation reaction and conditions were conducted in the same manneras in Comparative Example 1. The results are set forth in Table 1.

COMPARATIVE EXAMPLE 3

The zeolite catalyst used in this Comparative Example was 3.6 parts byweight of a commercially available zeolite. HY derived from 1/16″extrudate containing 80 wt % zeolite HY in an alumina binder. Thezeolite crystal size of this sample was 0.4-0.7 microns. The driedcatalyst was sieved to −18 to +25 mesh with a BET surface area of 564m²/g. The pretreatment and alkylation reaction and conditions wereconducted in the same manner as in Comparative Example 1. The resultsare set forth in Table 1.

EXAMPLE 1

This example illustrates the invention. One part of poroussilica-alumina with a silica/alumina ratio (“SAR”) of 5.1 wasimpregnated with 1.05 parts of a solution containing 45 parts by weightof NaOH and 55 parts of distilled water. The impregnated material afteraging was placed in an autoclave and heated at 85° C. for 24 hours. Thematerial was then washed with distilled water and dried at 120° C. toobtain a product containing >95% zeolite Y crystals having sizes of fromabout 25 to 100 nm.

The nanocrystalline zeolite Y as synthesized was ion-exchanged with amixture of LaCl₃ and NH₄NO₃ solution four times to remove sodium tobelow 0.2 wt %. After filtration and washing, the LaNH₄Y sample wasdried at 120° C. The dried powder was then mixed with appropriate amountof Nyacol alumina sol so that the final calcined product contained azeolite concentration of about 80 wt %. The paste was dried at 90° C.for 1 hr and then calcined in accordance with the following program: 2°C./min to 120° C., held for 1 hr, 2° C./min to 500° C., held for 2 hr,5° C./min cooling to room temperature.

The calcined pastes were ground and sieved to +20/−12 mesh size, ofwhich 4.0 parts on the dry basis was loaded into the alkylation reactorfor performance evaluation. The BET surface area of the final catalystwas 416 m²/g. The pretreatment and alkylation reaction conditions werethe same as above. This sample had an olefin breakthrough of 6.2 hr andthe alkylate had a RON of 100.2 before olefin breakthrough, as shown inTable 1.

EXAMPLE 2

The nanocrystalline zeolite Y as synthesized above in Example 1 wasion-exchanged to obtain LaNH₄Y as above. The binding, pretreatment andtest conditions were the same as in Example 1. The surface area of thissample was 409 m²/g. 4.0 Parts of the dried catalyst with a particlesize of −18 to +25 mesh were charged to the reactor. The sample had anolefin breakthrough of 6.0 hours and the alkylate product had a RON of100.3 before olefin breakthrough, as shown in Table 1.

EXAMPLE 3

The nanocrystalline zeolite Y as synthesized above in Example 1 wasion-exchanged to obtain LaNH₄Y as above. The binding and pretreatmentwere the same as in Example 1. The surface area of this sample was 389m²/g. The alkylation reaction conditions were the same as in Example 1except that the feed rate was 21.3 parts/hr. 4.0 Parts of the driedcatalyst with particle size of −18 to +25 mesh were charged to thereactor. The sample had an olefin breakthrough of 3.6 hours and thealkylate product had a RON of 100.4 before olefin breakthrough, as shownin Table 1.

EXAMPLE 4

The nanocrystalline zeolite Y as synthesized above in Example 1 wasion-exchanged to obtain LaNH₄Y as above. The binding, pretreatment andtest conditions were the same as in Example 1. The surface area of thissample was 413 m²/g. 4.0 Parts of the dried catalyst with particle sizeof −18 to +25 mesh were charged to the reactor. The sample had an olefinbreakthrough of 8.0 hours and the alkylate product had a RON of 99.5before olefin breakthrough, as shown in Table 1.

EXAMPLE 5

The nanocrystalline zeolite Y as synthesized above in Example 1 wasion-exchanged with a solution containing rare earth chlorides (“RECL₃”)and ammonium nitrate (NH₄NO₃) several times to reduce the sodium contentto below 0.2 wt % to obtain REY. The binding, pretreatment and testconditions were the same as in Example 1. The surface area of thissample was 396 m²/g. 3.6 Parts of the dried catalyst with particle sizeof −18 to +25 mesh were charged to the reactor. The sample had an olefinbreakthrough of 3.4 hours and the alkylate product had a RON of 100.5before olefin breakthrough, as shown in Table 1.

TABLE 1 Catalyst Life Example Catalyst (hrs) RON* RON** ComparativeCommercial 2.7 99.4 99.1 Example 1 zeolite Y Comparative Commercial 5.7101.0 98.1 Example 2 zeolite Y Comparative Commercial 3.5 101.0 99.3Example 3 zeolite Y Example 1 Nanocrystalline 6.2 102.5 100.2 zeolite YExample 2 Nanocrystalline 6.0 102.2 100.3 zeolite Y Example 3Nanocrystalline 3.6 101.8 100.4 zeolite Y Example 4 Nanocrystalline 8.0102.3 99.5 zeolite Y Example 5 Nanocrystalline 3.4 102.0 100.5 zeolite Y*After 1 hour of reaction **Before olefin breakthrough

The test results show the unexpected superiority of the nanocrystallinecatalyst of the present invention. For example, the average catalystlife of Comparative Examples 1 to 3 (conventional zeolite Y) at anaverage WHSV of about 0.25 parts of olefin per part of catalyst per hourwas 3.9 hours with an average RON before olefin breakthrough of about98.8. The average catalyst life of Examples 1 to 5 (nanocrystallinezeolite Y) at an average WHSV of about 0.26 parts of olefin per part ofcatalyst per hour was 5.36 hours with a corresponding average RON beforeolefin breakthrough of about 100.2.

While the above description contains many specifics, these specificsshould not be construed as limitations on the scope of the invention,but merely as exemplifications of preferred embodiments thereof. Thoseskilled in the art will envision many other possibilities within thescope and spirit of the invention as defined by the claims appendedhereto.

1. A process for alkylation of a hydrocarbon compound comprising. a) providing a catalyst including a zeolite Y having a crystal size of no more than 100 nm; b) reacting an alkylatable hydrocarbon with an alkylating agent in the presence of said catalyst under alkylation reaction conditions to provide an alkylate product, wherein the alkylatable hydrocarbon is paraffin and the alkylating agent is olefin.
 2. The process of claim 1 wherein the alcylatable hydrocarbon is isobutane and the alkylating agent is a butene.
 3. The process of claim 2 wherein the alkylate product comprises a gasoline having a research octane number of at least 99.5.
 4. The process of claim 1 wherein the step of providing the catalyst comprises: a) providing a porous inorganic oxide b) impregnating the porous inorganic oxide with a liquid solution containing an inorganic micropore forming directing agent which provides hydroxide ions, wherein the amount of liquid solution is no more than about 100% of the pore volume of the inorganic oxide, and the concentration of the micropore forming directing agent in the liquid solution ranges from about 25% to about 60% by weight, and c) heating the impregnated porous inorganic oxide at an elevated synthesis temperature for a duration of time sufficient to form a zeolite containing product.
 5. The process of claim 4 wherein the liquid solution of inorganic micropore forming directing agent is an aqueous solution of sodium hydroxide.
 6. The process of claim 1 wherein the zeolite Y has a crystal size of no more than about 50 nm.
 7. The process of claim 1 wherein the zeolite Y has a crystal size of no more than about 25 nm.
 8. The process of claim 1 wherein the zeolite Y has a sodium content of no more than about 0.2 wt%.
 9. The process of claim 1 wherein the zeolite Y has a sodium content of no more than about 0.1 wt%.
 10. The process of claim 1 wherein the zeolite Y has a sodium content of no more than about 0.05 wt%.
 11. The process of claim 1 wherein the catalyst includes a refractory oxide binder.
 12. The process of claim 11 wherein the refractory oxide binder comprises one or more oxides selected from the group consisting of silica, alumina, silica-alumina, titania and zirconia.
 13. The process of claim 1 wherein the zeolite Y includes one or more metals selected from the group consisting of Pt, Pd, Ir, Ru, Rh, Os, Fe, Co, Ni, La, Ce, Pr, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Cu, Ag and Au.
 14. The process of claim 1 wherein the zeolite Y includes lanthanum and wherein the lanthanum to zeolite mass ratio is at least about 0.04.
 15. The process of claim 1 wherein the zeolite Y has a mesopore to micropore volume ratio of from about 0.2 to about 0.6.
 16. The process of claim 1 wherein the catalyst has a BET surface area of at least about 275 m²/g, and wherein the zeolite Y has a rare earth metal component with a mass ratio of rare earth metal to zeolite of at least about 0.04, wherein the zeolite has a mesopore to micropore volume ratio of from about 0.2 to about 6.0, and a unit cell size of from about 24.6 Å to about 24.9 Å.
 17. The process of claim 1 wherein the alkylation reaction conditions include a temperature of from about −40° C. to about 250° C., a pressure of from about 1 bar to 100 bar, and a WHSV of from about 0.1 to about 500 hr⁻¹. 